In the last 10 years the phenomenon known bradyseism in the Campi Flegrei (CF), has been active, with different earthquakes swarms. This continuous low-magnitude seismic activity, has created problems in the densely populated area of CF, which includes the western portion of Naples. The seismic activity is accompanied by uprising of soils (about 2 cm/month). Some researchers are creating panic in the citizenry as they make hypothesis about the fact that a potential, catastrophic, Plinian eruption might occur any time. Such catastrophists hypothesize that bradyseism occurs due to up-rising of magma. The fact is that there is no proofs or evidence of such magma rising to explain the bradyseism phenomenon. With an international research group [1, and ref therein] we have made an interpretation of the bradyseism which occurs cyclically in the CF, at least in the last 4.000 years, never producing a catastrophic eruption. The only exception was the very small Monte Nuovo phreatic eruption of 1538 AD.

We obtained data during long-term monitoring of the CF volcanic district which has led to the development of a model based on lithological-structural and stratigraphic features that produce anisotropic and heterogeneous permeability features showing large variations both horizontally and vertically. These data are inconsistent with a model in which bradyseism is driven exclusively by shallow magmatic intrusions. Instead, CF bradyseism events are driven by cyclical magmatic-hydrothermal activity. Bradyseism events are characterized by cyclical, constant invariant signals repeating over time, such as area deformation along with a spatially well-defined seismogenic volume. These similarities have been defined as “bradyseism signatures” that allow us to relate the bradyseism with impending eruption precursors. Bradyseism is governed by an impermeable shallow layer (B-layer known as pozzolana), which is the cap of an anticlinal geological structure culminating at Pozzuoli, where maximum uplift is recorded. This B-layer acts as a throttling valve between the upper aquifer and the deeper hydrothermal system that experiences short (1-10² yr) timescale fluctuations between lithostatic/hydrostatic pressure. The hydrothermal system also communicates episodically with a cooling and quasi-steady-state long timescale (10³-10⁴ yr) magmatic system (at depth of 8 km) enclosed by an impermeable carapace (A layer).

Connectivity between hydrostatic and lithostatic reservoirs is episodically turned on and off causing alternatively subsidence (when the systems are connected) or uplift (when they are disconnected), depending on whether permeability by fractures is established or not. Earthquake swarms are the manifestation of hydrofracturing which allows fluid expansion; this same process promotes silica precipitation (and sulphides) that seals cracks and serves to isolate the two reservoirs.

Faults and fractures promote outgassing and reduce the vertical uplift rate depending on fluid pressure gradients and spatial and temporal variations in the permeability field. The mini-uplift episodes also show “bradyseism signatures” and are well explained in the context of the short timescale process.

This interpretation is supported by the fact that earthquake hypocenters at CF are never registered at depths between 4 and 8 km. 90% of the earthquake hypocenters (with M mostly between 1 and 2.5) occur at depths between 1.5 to 3.5 km. We know from deep boreholes that in the CF, that the B-layer; known as “pozzolana” is occurring at depth between 2-3 km [2]. The hydrothermal fluids, fracturing the impermeable layer, pass from lithostatic to hydrostatic pressure; hence they boil, depositing different sulphide mineralizations (pyrite, chalcopyrite, galena, scheelite and others) along the fractured system in the pozzolana B-layer [3-4]. When this occurs, the negative bradyseism begins, and the soil starts to go down slowly.

With the present state-of-the art knowledge of bradyseism, there is no evidence that a catastrophic plinian eruption might occur. Nevertheless millions of people are scared by the phenomenon. What should the Government do? 1. Proceed and prepare for a worst-case potential scenario as a precaution. As there is not evidence of any magma rising up at the moment, create ample, escape roads from which at least 1 million people should be able to escape quickly from the Red Zone of CF; 2. Establish an international panel of researchers and experts to advise the Government and citizenry of CF about seismic activity; 3. Carry out seismological screening of old houses in the Red Zone of CF and identify those not properly built to withstand the continuous small magnitude earthquakes continuously occurring in the Red Zone of CF.

The history and evolution of our species has always been closely linked with environmental factors. During the last years, the dramatic consequences of climate change and catastrophic events had an impact on humanity on a global level. In combination with methodologies from a variety of partner disciplines, Prehistoric Archaeology is the only academic field that analyses the interdependence between human societies and changing environmental conditions from a long-term perspective and based on the study of material culture. Therefore, it leads to a better understanding of the use of resources throughout time and space and is able to contribute to the solution of several problems that we are facing today. The last time human beings were subject to equally rapid changes, was towards the end of the last ice age (Late Glacial Interstadial), around 14,500 years ago. This period was marked by the disappearance of large reindeer herds in Central Europe and important innovations such as the widespread use of bow and arrow or domesticated dogs for hunting. The lecture gives an overview over the various ways in which interactions with natural resources have influenced human history and evolution. Based on several case studies, it shows how people adapted to new climatic conditions and challenges in the past. Finally, it presents strategies developed by prehistoric societies aimed at a more efficient and sustainable use of resources that could also lead to practical implications in the presence.      

Unusual microdiamonds discovered in metamorphic rocks of continental affinities during the 1990^th in Kazakhstan, China, Norway and Germany provided new geochemical data that led to revisions in the understanding of the plate tectonic subduction and exhumation processes [1,2,3,4].

Diamond, due to its chemical inertness, is considered the perfect “geological container” where gas, fluid, and solid inclusions can be preserved. High-resolution Scanning and Transmission Electron Microscopy, Focused Ion Beam technology, Synchrotron X-ray diffraction, Fourier Transformed Infra-Red, and Raman spectroscopic studies exemplify the remarkable interaction between 21st-century science and technology. These advancements have led to a paradigm shift regarding microdiamonds formation in geological environments of metamorphic belts previously believed to be “forbidden” for their crystallization.

Our studies revealed that nanoscale gas and fluid inclusions in microdiamonds consist of light and heavy elements such as  Cl, S, H, K, Cr, Ba, Ti, Pb, Mo, Co, Al [5,6]. The presence of the negative crystals of diamonds filled with a C-O-H fluid provided evidence that such a fluid was in equilibrium with the diamond at T= 800-1200^oC and P=7-9 GPa and it can be considered as the diamond-forming media [5,6]. Studies of microdiamond carbon isotopes characteristics suggest that the diamond was formed from “organic” carbon (average δ13C = -10 to – 33 ^o%) [6]. The measurements of noble gases in microdiamonds from the Kokchetav terrane of Kazakhstan indicate that the ³He/⁴He ratio is consistent with values associated with geochemical interactions between a continental crust slab and a mantle plume [6].

We have conducted a series of successful experimental reproductions of diamonds crystallization from C-O-H-rich fluids at geological conditions close to those of their host rocks [6]. Studies of microdiamonds from recently discovered UHPM terranes continue to release new geochemical observations on organic carbon cycling into deep mantle, geochemical crust-mantle interaction and rejuvenation of the mantle which are critical components for understanding of mantle dynamics.

Geopolymers are inorganic, polyaluminosilicate or chemically-bonded ceramics centered around the nominal formula M₂O•Al₂O₃•4SiO₂•11H₂O where M = Group I elements and the amount of water is variable, depending on the particle size and specific surface area of the aluminosilicate clay. They are refractory, inorganic polymers formed from both aluminum and silicon sources containing AlO₄^-and SiO₄ tetrahedral units, under highly alkaline conditions at ambient temperatures. Therefore, they are a rigid, hydrated, materials containing group I, charge-balancing cations which result in an amorphous, cross-linked, impervious, acid-resistant, 3-D structure.^1,2 Geopolymer composites are stable to 1000°C above which they crystallize into ceramic composites. They can be reinforced with ceramic, metal, polymeric or biological particulates, chopped fibers, weaves or meshes. They can be prefabricated in polymeric molds or 3D/4D printed. Other new inorganic polymers are being identified, such as acid-based Al₂O₃•SiO₂•P₂O₅ made by high shear mixing metakaolin with phosphoric acid; magnesium potassium phosphate (MgKPO₄); magnesium borate (MgO•B₂O₃); yttrium silicates and zinc silicates.³

To produce 1 ton of geopolymer liberates only 0.25 tons of CO₂ whereas 1 ton of CO₂ is liberated for manufacturing 1 ton of cement. In civil engineering, the term “geopolymers” refers to the product resulting from high shear mixing of class F fly ash mixed with ground, granulated, blast furnace, slag, waste products. The solid is also amorphous or crystalline, but it is based on the calcium silicate hydrate (CSH), C(A)SH, KASH, NASH) binder phases, forming cements not geopolymer. In this structure, the silicate or aluminate tetrahedra form 2D layers sharing only two or sometimes three corners, and are separated by layers of Ca(OH)₂. CSH is the main binder phase in Portland cement. One main difference between the cements versus geopolymers is that geopolymers are chemically stable up to 1,000°C, after which they crystallize into ceramic, retaining some mechanical strength. Cements contain significantly more water and steadily decompose with increasing temperature, losing their mechanical strength.⁴

Geopolymers have wide potential applications as: fire-resistant structures or coatings, corrosion-resistant coatings; stronger and tougher replacements for cements and concretes; ceramic composites exhibiting “graceful failure” or pseudo-ductility; geopolymers containing glass frit can undergo amorphous self-healing when heated below 950°C (ASH-G) or behave as amorphous, self-healed ceramics when crystallized above 950°C; ASH-G composites for molten salt encapsulation for thermal energy storage or micro nuclear reactor applications; (a, b,g and neutron) nuclear radiation shielding; electromagnetic pulse interference (EMI) shielding; water purification filters; refractory glues between ceramics, metals, glass and/or wood; non-burnable building insulation; as a substitute for cements or concrete when made from revalorized mine tailings; removal of heavy metals (As, Hg) or PFAS from water.

Composition, temperature and pressure are the main knobs to turn in synthesizing, characterizing, and using new materials. Though the geologic and planetary science communities have embraced pressure as a natural and necessary variable, it has been underutilized in materials research.  FORCE, the Facility for Open Research in a Compressed Environment, is a new initiative and laboratory at ASU, housing unique multianvil equipment and research. FORCE enables synthesis of relatively large samples over a wide pressure – temperature range   and combines both experimental and computational studies relevant to structure, bonding, and phase transitions. It is a user facility for the broad scientific community. FORCE and its capabilities will be described and several examples of current materials   research linking high pressure, thermochemistry, and important functional materials will be presented. Specifically, rare earth monoxides, metastable at ambient conditions, have been investigated, while current work focuses on sulfides, selenides, tellurides and arsenides. 

The compressional behaviour of microporous materials (in particular, zeolites and feldspathoids) compressed in a fluid can be substantially governed by the potential crystal-fluid interaction, due to the selective sorption of new molecular species (or solvated ions) through the structural cavities in response to the applied (hydrostatic) pressure.

When no crystal-fluid interaction takes place, the experimental findings and computational modelling performed so far show that the effects of the applied pressure, at the atomic scale, are mainly accommodated by the tilting of the (quasi-rigid) (Si,Al,P)O₄ tetrahedra, around the bridging oxygen atoms that act as hinges between tetrahedra [1]. Tilting of tetrahedra was proved to be the dominant mechanism at low-mid P-regime, then followed by distortion and compression of these polyhedra, which become dominant at the mid-high P-regime (i.e., once titling is not sufficient anymore to accommodate the deformation energy) [2]. Specific mechanisms of deformation at the atomic scale, in response to compression, are controlled by the topology of the framework of tetrahedra. For example, the continuous increase of channels ellipticity, with increasing pressure, is one of the most common deformation mechanisms in zeolitic frameworks, but inversion of ellipticity occurs only in response to a phase transition, with a drastic structure rearrangement (e.g., reconstructive in character). On the other hand, the compressibility of the cavities (in the form of channels or cages) is governed by the so-called extraframework population (made by ions and small molecules), leading to different bulk compressibility in isotypic structures [3]. The elastic parameters available for zeolites (natural or synthetic) show that microporosity does not necessarily imply high compressibility, and most of the zeolites appear to be less compressible than many other Crustal minerals [1,3]. A high compressibility is somehow expected for porous framework structures due to the tetrahedral tilting, but the bonding configuration between the framework of tetrahedra and the stuffed species affects the overall compressional behaviour, making this class of host-guest structures less compressible than other rock-forming silicates.

When compressed in penetrating fluids, some zeolites experience a P-induced intrusion of new monoatomic species or molecules from the fluids themselves. Materials having well-stuffed cavities at room P-T conditions tend to hinder the penetration of new species. Crystal-fluid interactions in zeolites have observed using pressure-fluids made by: monoatomic species (e.g., He, Ar, Kr, Xe), small (e.g., H₂O, CO₂) or more complex molecules (e.g., C₂H₂, C₂H₄, C₂H₆O, C₂H₆O₂, BNH₆, electrolytic MgCl₂·21H₂O solution), with potential geological and technological implications [4,5]. Diverse variables govern the P-mediated sorption phenomena: the “free diameters” of the framework cavities, nature and bonding configuration of the extraframework population, kinetic diameter of the potentially-penetrating molecules, rate of P-increase, temperature at which the experiment is conducted and surface/volume ratio of the crystallites under investigations.

Natural processes such as earthquakes, volcanism, and mountain building are driven by plate tectonics, which are fundamentally influenced by the deformation of rocks and minerals under various environmental conditions. Understanding the rheology of rock-forming minerals is thus crucial for deciphering the geodynamics of Earth. Our current understanding of mineral rheology is primarily derived from laboratory experiments and theoretical models based on simplified synthetic systems. However, the properties of minerals are significantly affected by structural defects and impurities, making the extrapolation to natural, chemically complex systems uncertain. Crystal defects such as dislocations, chemical impurities and vacancies play a crucial role in influencing the elastic properties of minerals and their rheology, introducing deviations from the idealized, flawless structure. These defects act as perturbations that impede the smooth transmission of mechanical forces within the crystal structure, consequently influencing its overall elasticity and, in turn, impacting the material's macroscopic mechanical properties. In addition to defects and vacancies, minerals often contain fluid, melt and solid inclusions that can reach significant volumetric abundances and strongly affect the elastic properties (and thus the mechanical properties and rheology) of the host crystal. The investigation of mineral inclusions does offer a unique opportunity to study their impact on the rheology of the host mineral in situ. This approach holds great potential for enhancing our comprehension of the rheology of mineral assemblages and, consequently, the dynamics of our planet.

The Alpine area presents many small copper deposits, mostly exploited since Late Medieval times. This led to the widespread assumption that these ores were exploited much before and that most circulating prehistoric metal objects were produced with local copper sources. This assumption was largely validated for the Bronze Age through the use of lead isotope tracers, and well supported by the archaeological and archaeometallurgical evidences. However, the scarcity of available lead isotope data for pre-Bronze Age metals precluded to date the reconstruction of the metal flow in the 4^th and 3^rd millennia BC [1-2]. 

Based on 49 new analyses of archaeologically important artefacts, it is now shown that the Northern Italian Eneolithic (or Copper Age, approximately 3500-2200 BC) includes three chronologically distinct periods of metal production: Balkanic, Tuscanian, and Alpine copper [3]. 

The Alpine ores were massively exploited only starting from the middle of the 3^rd millennium BC, in connection or slightly earlier than the Beaker event.
 

My research is focused on sustainable metallurgical processes that concerns energy, resource and environment. For metallurgical processes, one fundamental question is how much heat needed when reactants enter into the furnace regardless of minerals and electronic wastes. Calorimetry method is the main approach that I will use to explore the heat effect measurement in the metallurgical processes.

Geosystems especially in the Earth’s crust often feature rhythmic patterns such as banded formations, layered and folded structures, diapirs or cockade ores that can cover scales from just microns, and even sub-microns, up to several kilometers. This subject has been examined from a thermochemical-mechanical perspective since times. 

As well for a long time, physics was limited to characterizing continuous changes in closed systems. The concept of self-organization (I. Prigogine, 1977), however, enables to describe discontinuities as sequential spontaneous structure/texture formation. For this reason, the earlier approach in closed systems with given boundary conditions of existing "ideal gases" is abandoned and instead open systems with distributed components and properties (W. Ebeling, 1976) as well as available free energy are introduced. For allowing spontaneous structure/texture formation, the open systems should be far from thermodynamic equilibrium.

In closed systems, changes inevitably cause an increase in complexity and disorder (increase in entropy). Contrarily, the concept of self-organization in open systems lays the foundation for changes going together with increasing order and complexity at the same time, i.e. by means of export of entropy and energy dissipation. Here, phase transitions play an essential role. Precipitate patterns mediated by solute reactions have been discussed in detail since the 1980s (P. Ortoleva, 1982).  As a further characteristic of open systems, the scale invariance is formulated by H. Haken 1978 with his synergetics concept.

As the earth system is considered as an open system including geochemical processes and geomaterials of all scales that changes because of the supply and withdrawal of energy, ordered structures and patterns are typical features in geological systems.

In this talk, radiolarite, malachite, reef limestone and banded iron-manganese deposits will be addressed as illustrating examples. Using the example of a recent early diagenetic new mineral formation, the findings of experimental, theoretical, and numerical analyses will be discussed. Finally, generalized results will be considered for future investigation.

Planets that orbit stars other than our sun are called exoplanets and over 5,500 have been confirmed in our galaxy. Hot Jupiters are a type of exoplanet that orbit very close to their star and are tidally locked, with a permanent daytime and nighttime side. Being the hottest exoplanets, they emit the most radiation and thus are a prime target for the James Webb Space Telescope. Silicates are a ubiquitous feature of aerosols on hot giant exoplanets. [1] WASP 17-b is a hot Jupiter with an orbital period of 3.7 days whose atmosphere was recently observed by James Webb Space Telescope to be dominated by quartz (SiO₂) nanocrystals, although magnesium-rich silicates were expected to be seen. [2] In the brown dwarf VHS 1256-1257b, the best fit models for spectroscopic observations were clouds of enstatite (MgSiO₃), forsterite (Mg₂SiO₄), and quartz. [3] Despite key silicate features in spectroscopy, it is not possible to determine complete atmospheric composition and cloud formation by astronomical observations alone, and particle formation in atmospheres must be modeled. Major factors in modeling atmospheres are nucleation and condensation, which are exponentially dependent on the species’ surface energy, with higher surface energies drastically hindering nucleation rates. Although the need for  reliable  surface energy measurements is evident, surface energies of several key species in hot giant exoplanets are not yet constrained by experiment. In this work, surface energies of likely exoplanet atmosphere condensates, including zinc sulfide (ZnS), crystalline, and amorphous enstatite were measured using oxide melt solution calorimetry of appropriate nanoparticles. These are then input into a nucleation code that gives nucleation rates for these species. [4,5] The surface energy of crystalline SiO₂ is much lower than that of the crystalline magnesium-rich silicates, supporting the observation of silica in the atmosphere of WASP-17b, while the surface energy of amorphous enstatite is similar to that of quartz. [4,6] This suggests that initial nucleation of MgSiO₃ in VHS 1256-1257b could form the amorphous phase. This research provides experimental surface energy data of high relevance to a broad range of exoplanet atmospheres.

Framework structures, which feature three-dimensional networks of relatively rigid polyhedral units that share corners with one another, encompass a wide range of natural and synthetic compounds of importance in Earth science, chemistry, physics, and materials science. Examples include feldspars, zeolites, garnets, perovskites and hybrid materials such as metal-organic frameworks (MOFs). The inherent flexibility of the framework gives rise to many interesting phenomena that control the stabilities of the materials.  These phenomena include extensive polymorphism, negative volumes of fusion, very low to negative thermal expansion, a P-T region of pressure induced amorphization, and polyamorphism. These properties serve as inspirations that form the basis of many technological materials such as photovoltaics, sensors, catalysts, lasers, molecular sieves, etc. The Ross group studies the structure-property relations of framework materials using a combination of methods including X-ray diffraction, Raman spectroscopy and inelastic neutron spectroscopy to explore how the flexible structural framework is related to their thermodynamic, elastic and physical properties[1-5]. This talk will present an overview of how structural changes influence mechanical functionality and ongoing ultimately lead to the development of novel materials based on this important group of materials.

Nanostructured transition metal nitrides represent a sustainable alternative to conventional materials in a variety of applications, including catalysis, coatings, electrochemical devices, and lithium-ion batteries [1]. Nanoparticles exhibit thermodynamic parameters that can differ significantly from those of bulk materials due to the decrease in dimension [2] and dependence of energetic stability on the surface energy. The investigation of how the thermodynamic parameters of transition metal nitrides differ between bulk and nanoparticles provides the foundation for optimizing these materials for diverse applications. However, compared to other properties (e.g., magnetic, conductive, electronic) that have been measured, thermodynamic investigation is still in its nascent stages. In this study, we employ high temperature oxidative melt solution calorimetry [3] and differential scanning calorimetry to ascertain thermodynamic properties (enthalpy of formation, surface energetics and enthalpy of decomposition) and to identify and discuss stability differences between bulk and nanophases as well as trends among different transition metal (Ti, Fe, Co, and Ni) nitride phases.

Superconductivity in the vicinity of room temperature has the potential to revolutionize numerous technologies and sustainability as well as our understanding of condensed matter. Zero electrical resistance and expulsion of magnetic field below a critical temperature are critical tests of superconductivity. As for the original high-T_c cuprate superconductors, accurate crystal structures are also required for complete characterization of the materials [1]. Inspired by theoretical predictions for hydrogen-rich materials under pressure [2], previous work from our group has established the existence of near-room temperature superconductivity at megabar pressures [3], now reproduced by numerous other groups [4]. Recently reported evidence for superconductivity at ambient P-T conditions in nitrogen-doped lutetium hydride (Lu-N-H) has been promising but controversial [5]. Our group has conducted independent electrical resistivity and magnetic susceptibility measurements on the material that confirm the remarkable properties of the material as well as the difficulty of synthesis [6]. First-principles DFT and DFT+U calculations provide important insights into the behavior of this remarkable class of materials [7]. There are prospects for similar high T_c superconductivity in related compounds, including complex quaternary and higher order chemical systems.